Abstract
A relationship between the overall electrolytic deuterium separation factor of the hydrogen electrode reaction and the separation factors of the steps that constitute the reaction is formulated for the discharge-combination route, without assuming an overwhelming unique rate-determining step. This is utilized for the quantitative interpretation of sharp variation of the cathodic deuterium separation factor with overpotential observed on Pt and Au in aqueous H 2SO 4 and an insignificant variation on Ni in alkaline solutions. The variation on Pt and Au is interpreted in terms of change with cathodic overpotential of the mechanism from the rapid discharge—slow combination to the slow-discharge. The variation on Ni is expected to be significant only in the anodic region.
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